An equation by D. P. H. Smith predicts the capillary voltage required for the onset of electrospray (ES). For different solvents the voltage increases with the square root of the surface tension. Water requires a potential that is 1.8 times higher than that for methanol. This is verified experimentally. The higher potential required for water leads to ES in the presence of corona electric discharge. For low total ES plus corona currents, the electrosprayed analyte ion intensity is not adversely affected by the presence of discharge. At high total currents, there is a large decrease of analyte sensitivity. The sensitivity decrease is probably due to adverse space charge effect at high currents. The discharge can be suppressed by adding sulfur hexafluoride to the ambient gas. Both sensitivity and signal stability are improved. However, the sensitivity still remains lower by a factor of - 4 relative to that observed with methanol. This is attributed to lower efficiency of gas-phase ion formation from charged water, relative to methanol, droplets. © 1991 American Society for Mass Spectrometry.
Ikonomou, M. G., Blades, A. T., & Kebarle, P. (1991). Electrospray mass spectrometry of methanol and water solutions suppression of electric discharge with SF6 gas. Journal of the American Society for Mass Spectrometry, 2(6), 497–505. https://doi.org/10.1016/1044-0305(91)80038-9